Static secondary ion mass spectrometry has been used to investigate orientation effects at the surfaces of segmented polyetherurethanes. The presence of hard segments at the polymer surface was found to be dependent upon the sample preparation method. Spin casting can produce a larger hard segment content than straightforward solvent evaporation, and films produced by spin casting slowly reorganize to remove hard segments from the top 10 Angstrom or so. The occurrence of such effects is restricted to polymers with high polypropylene oxide content in the soft segment and a reasonably large (above about 2500) soft segment molecular weight.